Manufacture of organic substitution derivatives of cellulose



ensures se s as less @F @BEGAMG SUBSTITU- fiiQN @F @FJLEoSE.

Zireytn-s, London, land No montage Application November lit; 19%, adti lid'iu in Great toin Eeeember ices is tor. sec-rot) w invention relates to the manufacture or new cellulose derivatives and more particularly new cellulose derivatives containing nitrogen,

According to the present invention cellulose or materials containing cellulose or cellulose derivatives containing free hydroxy groups are treated with esterifying or etherifyine agents containing the nitrile group. GM. I have found that by these means valuable cellulose derivatives may be produced, which may be converted, e. g. by reduction or by hydration, into other valuable nitrogen containing" cellulose derivatives. nitrogen containing cellulose derivatives of the present invention have an affinity for acid wool i As examples of suitable agents for the manufacture or the newcellulose derivatives the fol-' lowing may be mentionedzchlor-acetonitrile, "cyanacetyl chloride, isor B-chlor propionitrile or i go' their homologues or derivatives,

I have found that the treatment of thecellulose with the nitrile-containing esterlfying or etheriiying agents may be carried out by methods analogous to those known for the manufacture of the ordinary esters or ethers of cellulose. The cellulose may be previously or simultaneously alkalized, for example with caustic soda or caustic potash. In the case of cyanacidyl halides the treatment may be eiiected in the presence of pyridine or other organic bases and in particular strongbasessuch as N-methyl piperidlne, dimethyl-n-hexylamine, dimethyl aniline and the like. Inorganic alkalies are-preferably employed in high-concentration so as to obtain highly etherlfled or esterified derivatives. The

lnventiondoes not, however, exclude the introduction of relatively low proportions of ether or ester group into the cellulose, for example proportions of the order of one ether group in one cellulose molecule, calculated on the Co formula, or even less. The caustic soda or caustic potash may, for example, be employed in a concentration of at least and preferably in suflicient quantity to form a saturated solution in any 45 water which may be present. In the case of forming cellulose ethers I have found that particularly useful derivatives are obtainable by emw ploying caustic soda in a proportion at least'equal we times theweight or any water'present. The

.50 water ispreierably present in a quantity less than 4 times the weight of the cellulose; and may be as low as 1% or times its weight or less. As an alternative the water maybe wholly or in part replaced by organic liquids, e, g. alcohol,

ether, benzene or toluene, and such me may 5 be present in a large proportionso that the reaction is conducted in suspension.

As initial materials for treatment according to the present invention any desired cellulosic ma= terials may beused, for example cotton cellulose 10 or its near conversion products for example the regenerated cellulose obtained by the viscose yprocess'or wood pulps,preferably chemical wood pulps, such as sulphite pulp, soda pulp or sulphate pulp from which the lignin, pentosan, resin 15 and like constituents have been substantially removed. The invention further contemplates the treatment of cellulose derivatives containing free hydroxy groups, for example methyl, ethyl or other alkyl, or aralkyl, hydroxyalkyl or car- 20' boxyhlkyl derivatives .of cellulose or acetyl or other acidyl derivatives of cellulose, and it may be pointed out that the invention is of importance in the treatment of such materials since it enables mixed derivatives to be produced which 25 while retaining the desirable properties of the known cellulose derivatives exhibit also an atonity for acid dyes. Such mixed derivatives may likewise be produced by treatment according to the present inventionof a cellulose or cellulose 30 containing material followed by etherlfication or esteriflcation to introduce the other desired radicles.

The esteriflcation or etheriflcation characteristic of the invention may be efiected as prevl- 35 ously indicated by methods analogous to those used for the ordinary esters and others. For instance in the case of producing ethers the cello. lose may be kneaded ,with caustic alkali solution or may be first moistened with, the desiredrlo -a strong base such as a methyl piperidine or dimethyl-n-hexylainine. The treatment may he carried out in two or more stages; either the base, 5

organic or inorganic, or the etherii'ying or eateriiying agent beingbrought to reaction with the cellulose in portions.

The invention includes also the production of mixed etheresters oi cellulose by treating the cellulose simultaneously or separately with a nitrile-containing etheriiying agent and a nitrilecontaining esteriiying agent.

As previously indicated, a further important feature of the invention comprises the conversion 01' the new nitrile-containing cellulose derivatives intoother nitrogen containing derivatives of cellulose. 'For example the new derivatives may be treated with reducing agents, e. g. with sodium amalgam in .boiling alcohol or boiling aqueous alcohol, to produce the corresponding amino derivatives of cellulose. Again the nitrile-containing cellulose derivatives may be hydrated or hydrolyzed, for example by boiling with water un der pressure or by boiling with water in presence of catalysts, such as hydrochloric acid or hydrogen peroxide or hydrogen peroxide in conjunction with sodium peroxide, to obtain bodies of a simi- .lar type to. those produced accordingto British application No. 36474/29 dated 28th November, 1929 corresponding to'U. S.- application S. No.

492,363 flied October 30, 1930 in which amino the present invention which contain primary or secondary amino groups may .be alkylated, aralkylated or 'acylated, ior instance by treatment with an alkyl or aralkyl halide or an acidyl chloride or anhydride.

it in any way:-

v The following examples show the'best methods known to me for carrying the invention-into etiect, but they are not to be considered as limiting Example 1 162 parts of cotton linters or purified wood pulp are suspended in .a mixture oi. 500 parts of dimethyl-n-hexylamin'e and 300 parts of nitrobenzene and a. solution of 350 parts of cyanacetyl chloride in a'iurther 1000 parts-oi nitrobenzene is added slowly while keeping the temperature at.

between and C. Ai'ter "l to 2 hours or when there is no iurther-evolution oi heat, the cellulose derivative produced is separated fromthe. reaction mixture and washed with alcohol. It is soluble in glacial acetic acid and acetylene 'tet rachioride and is insoluble in alcohol, ether and water. i

" Example 2 162 parts of cotton linters or purified wood pulpare treated 'with a mixtureoi parts oi cyanacetylchloride, parts'o! dimethyl-n-hexylamineand 1000parts'oi' glacial acetic acid. When the reaction is complete a-mixture o1 250parts oi .acetic anhydride, 200 parts of aceticac'id and 16-20'parts of sulphuric acid are added; the reactionmixturebeing then cooled, some to main.-

tain a temperature 01 15, to 25 C. ".When solu-] tion is complete, the-mixed cellulose derivative may 'be precipitated therefrom by addition of water, ether or othe? nonesolvent or may be ripened in solution as is usual in the cellulose acetate art. I

' Example 3 162 parts oi cotton linters or purified wood pulp are impregnated with 320 parts of a 50% aqueous solution oi. caustic soda, the whole being kneaded together for about 2 hours. period to 225 parts of chloracetnnitrile are added, the mass being kneaded for a further 2 to 3 hours at a temperature which may vary between ordinary temperature and 60C. A further 240 parts 01' powdered caustic soda are then worked in and subsequently 250 parts oi chloracetonitrile, the temperature of the reaction being then carried'to 50-l00 C. A further etheriilcation step may then be applied with an additional parts oi caustic soda and 200 parts of chloracetonitrile. At the end oi the reaction, the product is washed free from reagents and dried. It is soluble in glacial acetic acid and insoluble in ether.

Example 4 100 parts oi the product obtained according to Example 1 or 3 is treated with about 100 parts oi Attheendoithis.

a "20 volume" solution of hydrogen peroxide. 25

After a short time 15-20 parts of sodium peroxide are added with stirring or kneading, the addition being sufliciently gradual to prevent undue rise-- of temperature and cooling being applied it necessary so that the temperature does not exceed about 35-40 C. when the evolution of oxygen has ceased, gentle heat is applied for a short time and the products then cooled and washed with water.- The products are soluble in aqueous acetone and acetic acid and in fact are similar in properties to-those obtained according to British application No. 36474/29 dated 28th November,

' 1929 .corresponding to U. 8. application 8. No.

sun further by means of moderately concentrated or concentrated mineral acids. Thus the product obtained according to Example 3 may be gently warmed at about 40-50 C. with 20-25% aqueous hydrochloric acid or with 30.40% aqueous sulphuric acid, when products are ob-' tained which are moresoluble in aqueous reagents, e. g. 50% acetone or 50% alcohol, thanare the products obtained with hydrogen peroxide.

By continuing the treatments, say from 3-6 hours,

the nitrogen content. of the cellulose derivative.

continually diminishes. The product, which is at least partly soluble in aqueous alkali, probab contains iree carboxylic acid groups.

Example 5 The product obtained according to Example 3 is suspended in 10 times its weight of amyl alcohol and-the whole heated until just short of boiling temperature. Sodium in the torm of a 10% amalgam is then added gradually during 2 hours until the totaliquantity 01 sodium added is about The products contain nitrogen 0.5 to 0.75 times the weight of the cellulose derivative used. The liquor is then boiled for halt an hour, cooled and the cellulose derivative separatedand washed with aqueous alcohol. It has an ainnity for acid dyestuiismore pronounced thantheproductsoihxamplat I.

What I claim and Patent is:- I l I 1. Process tor the production of new cellulose derivatives, which comprises treating cellulose with halogen containing substitution agents which contain the radicle desire to secure by Letters 2. Process for the production of new cellulose derivatives, which comprises treaties, cellulose with halogen containing esterii'yiiis' agents which contain the radicle 3. Process for the production of new cellulose" derivatives, which comprises treating cellulose with halogen containing 'etheriiyine agents which contain the rssllcie -c c 5N 4. Process for the production of new cellulose derivatives, which comprises treating; ceiimme with halogen which contain the reelicle in the presence o! a strong beset v 5. Process for the production of new cellulose derivatives, which comprises treatises cellulose with halogen containing esteriiying scents which contain the redicle -c c an r in the presence of a. strong; oreanie lease.

6. Process for the production of new cellulose derivatives, which comprises treating cellulose with halogen containing esterifyinz agents which contain the radicle V I -c 0 EN in the presence of caustic al.

- 7. Process'tor the production of newcelluiose derivatives, which comprises treating cellulose with halogen containing substitution agents which contain the radlcie and reducing product.

' with halogen containing esterlfying agents which containing substitution agents 8. Process for the production of new cellulose derivatives, which comprises treating cellulose with halogen containing substitution agents which containthe radicle and hydrolvzing the product;

9. Process for the production of new cellulose derivatives, which comprises treating cellulose with halogen containing etheriiyine secrets which contain the rerlicle -c a c 5N v I and-hydrolyzing the product.

13. Organic substitution @erivatiyes of cellulose containing the'mdicle Cw -0 a c 5N l4. geliuiose esters containing the radicle I 7@\C;N I 45 1'5. Cellulose ethers containing the radicle i-CN may Dams.

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